EP0025246A1 - Process for preparing a fireproofing composition from sodium antimonate, and composition so obtained - Google Patents

Process for preparing a fireproofing composition from sodium antimonate, and composition so obtained Download PDF

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Publication number
EP0025246A1
EP0025246A1 EP80200808A EP80200808A EP0025246A1 EP 0025246 A1 EP0025246 A1 EP 0025246A1 EP 80200808 A EP80200808 A EP 80200808A EP 80200808 A EP80200808 A EP 80200808A EP 0025246 A1 EP0025246 A1 EP 0025246A1
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EP
European Patent Office
Prior art keywords
mixture
antimonate
sodium antimonate
sodium
acid
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EP80200808A
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German (de)
French (fr)
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EP0025246B1 (en
Inventor
Fulvio Contin
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Metallurgie Hoboken-Overpelt SA
Societe Generale Metallurgique de Hoboken SA
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Metallurgie Hoboken-Overpelt SA
Societe Generale Metallurgique de Hoboken SA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/004—Oxides; Hydroxides; Oxyacids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/02—Antimonates; Antimonites
    • C01G30/023—Antimonates; Antimonites of ammonium, alkali or alkaline-earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content

Definitions

  • the present invention relates to a process for preparing a flame retardant composition from sodium antimonate.
  • This known method has the drawback of being ill-suited to the treatment of sodium antimoniates obtained at high temperature such as the antimonate obtained as a by-product in the alkaline refining of lead according to the Harris method, such antimoniates being very resistant to crushing and therefore difficult to grind.
  • the flame retardant composition obtained by this known process consists essentially of sodium antimonate and is free of antimony oxide, is also disadvantageous, since a mixture of sodium antimonate and oxide of antimony has better flame retardant properties than sodium antimoniate as such (see US Patent No. 3,723,139).
  • the object of the present invention is to provide a method which avoids the above drawbacks.
  • the sodium antimonate is reacted with an acid solution so as to transform a fraction of the antimonate in pentavalent antimony oxide, thus producing a mixture consisting of pentavalent antimony oxide and sodium antimonate, the mixture thus produced is separated from the solution, this mixture is dried and sprayed.
  • any sodium antimonate can be used, whether obtained at high temperature or by the wet method.
  • Any acidic solution which reacts with sodium antimonate can be used to form antimony oxide.
  • an aqueous solution of hydrochloric acid and / or sulfuric acid and / or nitric acid is preferably used, with a concentration advantageously between 1 and 5 N.
  • the antimoniate is reacted with an amount of acid ranging from 1 to 1.35 times the stoichiometric amount, so as to convert at least 60 and, preferably, at least 95% of the antimonate to oxide.
  • the reaction can be carried out at any temperature between the freezing point and the boiling point of the acid solution, but it is preferably carried out at room temperature (18-25 ° C), because of a on the one hand it is advantageous to convert the antimoniate as much as possible into oxide and on the other hand, it has been found that for the same antimonate: acid ratio and the same reaction time the conversion rate of the antimonate into oxide is much higher at room temperature than at high temperature.
  • reaction time this is preferably sufficient for the reaction to reach equilibrium. A duration of 1 to 3 hours has proved satisfactory.
  • the reaction is advantageously carried out by suspending the sodium antimonate in the acid solution.
  • Content sodium antimonate in the suspension is preferably more than 200 g / l; otherwise, the operating costs of the process become too high. This content is preferably less than 900 g / l when using a sulfuric acid solution, and less than 750 g / l when using a hydrochloric acid or nitric acid solution, because otherwise, the suspension becomes pasty.
  • the mixture of antimony oxide and antimonate resulting from this suspension reaction is then separated from the solution, for example by filtration, and washed first with a dilute solution of a mineral acid, preferably from 1 to 4 N, and then with enough water to remove the acid. If washed directly with water, the sodium content of the product obtained increases significantly.
  • a dilute solution of a mineral acid preferably from 1 to 4 N
  • the washing and drying of the washed mixture can be carried out simultaneously. This is how a powder is obtained directly, which passes almost the entire 325 mesh screen, when the washed mixture is treated in a spray dryer. It should be noted that the grain size of a powder having passed the 325 mesh sieve is less than 44 ⁇ m.
  • Drying and spraying of the washed mixture can also be carried out consecutively.
  • the washed mixture can first be dried, for example in an oven, and then disintegrate the dried mixture, for example in a hammer mill; in this way, a powder is also obtained, which passes almost in its entirety the 325 mesh screen. If we want to obtain a finer powder, we will treat the dried mixture in an air jet mill, thus producing a powder made up of particles whose particle size spectrum is very narrow (0 to 2 ⁇ m) and whose average size grains is approximately 1 ⁇ m.
  • an oxidizing agent preferably hydrogen peroxide
  • H 2 0 2 is advantageously added to the suspension in an amount sufficient to put these impurities in solution.
  • the invention also relates to the flame retardant compositions obtained by the process according to the invention as well as the flame retardant products by addition of these flame retardant compositions.
  • the starting material is a wet sodium antimonate obtained as a by-product in a lead refining plant according to the Harris process.
  • This wet antimonate (10 to 12% by weight of water) contains in the dry state, in% by weight: 48.8 Sb; 9.32 Na; 21.88 H 0 of crystallization.
  • This example relates to the preparation of a flame retardant composition from the above starting material (antimoniate ex Harris) by the process of the prior art mentioned above and consisting in grinding the antimonate so as to obtain a very fine antimonate .
  • the starting material is first dried and then calcined at 280 ° for 4 hours to remove most of the water of crystallization.
  • the calcined antimony which contains 57.74% by weight of antimony, is then pulverized in an air jet mill type MC-200 KX from the company Micro Grinding Ltd. from Switzerland. We operate with a pressure of 6.5 bar and the device, which is self-classifying, delivers 5 kg of powder per hour (average grain size: 1 ⁇ m).
  • the flame retardant properties of this powder are evaluated by the standardized method of determining the oxygen index.
  • this powder is added to a plastic material consisting of 100 parts of PVC (Solvic 271 GA from the company Solvay), 36 parts of dioctylphthalate, 5 parts of tribasic lead sulphate and 1 part of calcium stearate .
  • This material has an oxygen index of 30.3.
  • This example relates to the preparation of a flame retardant composition from the above starting material (antimoniate ex Harris) by the process of the present invention.
  • the washed cake is dried in an oven. 5.2 kg of dry product are obtained, titrating 63.81% of Sb, 0.18% of Cl and 0.08% of Na. This product contains 0.67% by weight of NaSbO and 99.33% by weight of Sb 2 0 5 (calculated values).
  • This product is sprayed in the air jet mill of Example 1, at a pressure of 6.5 bar.
  • the device delivers 30 kg of powder per hour.
  • This example like example 2, relates to the preparation of a flame retardant composition from the aforementioned starting material (antimoniate ex Harris) by the process of the present invention.
  • the dried product After the dried product has disintegrated in a hammer mill, it is sieved through a 325 mesh screen.
  • the fraction having passed the sieve (99.7%) is used to flame retard the PVC-based plastic material of Examples 1 and 2.
  • To this plastic material 5.4% by weight of this fraction having passed the sieve is added. 325 meshes, thereby producing a PVC-based plastic material having the same Sb content as those of Examples 1 and 2.
  • This plastic material has an oxygen index of 31.6. Although 0.7 units lower than that obtained in Example 2, this index, obtained using a fairly coarse flame retardant composition, is still 1.3 units higher than that obtained in Example 1 with the very fine antimony.
  • This example also relates to the preparation of a flame retardant composition from the above-mentioned starting material (antimoniate ex Harris) by the process of the present invention.
  • This product is sprayed in the air jet mill of Example 1, at a pressure of 6.5 bar.
  • the device delivers 30 kg of powder per hour.
  • the first portion is filtered and the filter cake is washed with 1.27 l of water.
  • the washed cake is dried in an oven. 0.252 kg of dry product is obtained, titrating in% by weight: 63 Sb, 1.92 Na and 0.3 Cl.
  • This product contains 16.1% by weight of NaSbO 3 and 83.9% by weight of Sb 2 O 5 (calculated values).
  • the second portion is filtered and the filter cake is washed first with 0.45 1 of an aqueous solution of 0.16 1 of 12 N HCl per liter and then with 1.13 1 of water.
  • the washed cake is dried in an oven. 0.294 kg of dry product is obtained, titrating in% by weight: 63.48 Sb, 0.43 Na and 0.18 Cl.
  • This product contains 3.6% by weight of NaSbO 3 and 96.4% by weight of Sb 2 O 5 (calculated values).
  • ex Harris antimonate used as starting material in these examples is an antimonate obtained at high temperature and therefore not very reactive. It therefore goes without saying that any sodium antimoniate can be treated by the process of the present invention, whether it is obtained at high temperature or by the wet method.

Abstract

On fait réagir de l'antimoniate de sodium avec une solution acide de façon à transformer une fraction de l'antimoniate en oxyde d'antimoine pentavalent, en produisant ainsi un mélange d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, on sépare le mélange ainsi produit de la solution, on sèche et on pulvérise ce mélange. La poudre ainsi produite est un ignifuge remarquable.Sodium antimonate is reacted with an acid solution so as to convert a fraction of the antimonate to pentavalent antimony oxide, thereby producing a mixture of pentavalent antimony oxide and sodium antimonate, separates the mixture thus produced from the solution, it is dried and this mixture is sprayed. The powder thus produced is a remarkable flame retardant.

Description

La présente invention se rapporte à un procédé pour préparer une composition ignifuge à partir d'antimoniate de sodium.The present invention relates to a process for preparing a flame retardant composition from sodium antimonate.

Un tel procédé est connu par les brevets américains Nos 3.892.667 et 3.897.389. Selon ce procédé connu, on broie l'antimoniate de façon à obtenir un antimoniate très fin qui constitue alors la composition ignifuge.Such a process is known from American patents Nos. 3,892,667 and 3,897,389. According to this known process, the antimonate is ground so as to obtain a very fine antimonate which then constitutes the flame retardant composition.

Ce procédé connu présente l'inconvénient de se prêter mal au traitement d'antimoniates de sodium obtenus à haute température tels l'antimoniate obtenu en tant que sous-produit au raffinage alcalin du plomb selon le procédé Harris, de tels antimoniates étant très résistants à l'écrasement et, partant, difficilement broyables.This known method has the drawback of being ill-suited to the treatment of sodium antimoniates obtained at high temperature such as the antimonate obtained as a by-product in the alkaline refining of lead according to the Harris method, such antimoniates being very resistant to crushing and therefore difficult to grind.

Le fait que la composition ignifuge obtenue par ce procédé connu est constituée essentiellement d'antimoniate de sodium et est exempte d'oxyde d'antimoine, est également désavantageux, étant donné qu'un mélange d'antimoniate de sodium et d'oxyde d'antimoine possède de meilleures propriétés ignifuges que l'antimoniate de sodium tel quel (voir brevet américain n° 3.723.139).The fact that the flame retardant composition obtained by this known process consists essentially of sodium antimonate and is free of antimony oxide, is also disadvantageous, since a mixture of sodium antimonate and oxide of antimony has better flame retardant properties than sodium antimoniate as such (see US Patent No. 3,723,139).

Le but de la présente invention est de procurer un procédé qui évite les inconvénients ci-dessus.The object of the present invention is to provide a method which avoids the above drawbacks.

Selon l'invention, on fait réagir l'antimoniate de sodium avec une solution acide de façon à transformer une fraction de l'antimoniate en oxyde d'antimoine pentavalent, en produisant ainsi un mélange constitué d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, on sépare le mélange ainsi produit de la solution, on sèche et on pulvérise ce mélange.According to the invention, the sodium antimonate is reacted with an acid solution so as to transform a fraction of the antimonate in pentavalent antimony oxide, thus producing a mixture consisting of pentavalent antimony oxide and sodium antimonate, the mixture thus produced is separated from the solution, this mixture is dried and sprayed.

Comme antimoniate de départ, on peut utiliser tout antimoniate de sodium, qu'il soit obtenu à haute température ou par voie humide.As the starting antimonate, any sodium antimonate can be used, whether obtained at high temperature or by the wet method.

On peut utiliser toute solution acide qui réagit avec de l'antimoniate de sodium pour former de l'oxyde d'antimoine. Pour des raisons économiques on utilise cependant, de préférence, une solution aqueuse d'acide chlorhydrique et/ou d'acide sulfurique et/ou d'acide nitrique, d'une concentration comprise avantageusement entre 1 et 5 N.Any acidic solution which reacts with sodium antimonate can be used to form antimony oxide. However, for economic reasons, an aqueous solution of hydrochloric acid and / or sulfuric acid and / or nitric acid is preferably used, with a concentration advantageously between 1 and 5 N.

Quant au rapport antimoniate : acide à mettre en oeuvre, il va de soi que celui-ci dépend de la fraction de l'antimoniate que l'on désire transformer en oxyde. Avantageusement, on fait réagir l'antimoniate avec une quantité d'acide allant de 1 à 1,35 fois la quantité stoechiométrique, de façon à transformer au moins 60 et, de préférence, au moins 95 % de l'antimoniate en oxyde.As for the antimonate: acid ratio to be used, it goes without saying that this depends on the fraction of the antimonate which it is desired to transform into oxide. Advantageously, the antimoniate is reacted with an amount of acid ranging from 1 to 1.35 times the stoichiometric amount, so as to convert at least 60 and, preferably, at least 95% of the antimonate to oxide.

La réaction peut être effectuée à une température quelconque entre le point de congélation et le point d'ébullition de la solution acide, mais elle est effectuée, de préférence, à la température ambiante (18 à 25°C), parce que d'une part il est avantageux de transformer l'antimoniate autant que possible en oxyde et que d'autre part, il a été trouvé que pour un même rapport antimoniate : acide et une même durée de réaction le taux de transformation de l'antimoniate en oxyde est beaucoup plus élevé à la température ambiante qu'à haute température.The reaction can be carried out at any temperature between the freezing point and the boiling point of the acid solution, but it is preferably carried out at room temperature (18-25 ° C), because of a on the one hand it is advantageous to convert the antimoniate as much as possible into oxide and on the other hand, it has been found that for the same antimonate: acid ratio and the same reaction time the conversion rate of the antimonate into oxide is much higher at room temperature than at high temperature.

Quant à la durée de réaction, celle-ci est, de préférence, suffisante pour que la réaction puisse atteindre l'équilibre. Une durée de 1 à 3 heures s'est avérée satisfaisante.As for the reaction time, this is preferably sufficient for the reaction to reach equilibrium. A duration of 1 to 3 hours has proved satisfactory.

La réaction est avantageusement effectuée en mettant l'antimoniate de sodium en suspension dans la solution acide. La teneur en antimoniate de sodium de la suspension est, de préférence, supérieure à 200 g/l; autrement, les frais d'exploitation du procédé deviennent trop élevés. Cette teneur est, de préférence, inférieure à 900 g/1, lorsqu'on utilise une solution d'acide sulfurique, et inférieure à 750 g/1, lorsqu'on utilise une solution d'acide chlorhydrique ou d'acide nitrique, parce qu'autrement, la suspension devient pâteuse.The reaction is advantageously carried out by suspending the sodium antimonate in the acid solution. Content sodium antimonate in the suspension is preferably more than 200 g / l; otherwise, the operating costs of the process become too high. This content is preferably less than 900 g / l when using a sulfuric acid solution, and less than 750 g / l when using a hydrochloric acid or nitric acid solution, because otherwise, the suspension becomes pasty.

Le mélange d'oxyde d'antimoine et d'antimoniate résultant de cette réaction en suspension est alors séparé de la solution, par exemple par filtration, et lavé d'abord avec une solution diluée d'un acide minéral, de préférence de 1 à 4 N, et ensuite avec suffisamment d'eau pour éliminer l'acide. Si on lave directement à l'eau, la teneur en sodium du produit obtenu augmente sensiblement.The mixture of antimony oxide and antimonate resulting from this suspension reaction is then separated from the solution, for example by filtration, and washed first with a dilute solution of a mineral acid, preferably from 1 to 4 N, and then with enough water to remove the acid. If washed directly with water, the sodium content of the product obtained increases significantly.

Le séchage et la pulvérisation du mélange lavé peuvent être effectués simultanément. C'est ainsi que l'on obtient directement une poudre, qui passe pratiquement dans son entièreté le tamis de 325 mailles, lorsqu'on traite le mélange lavé dans un séchoir-atomiseur. Il est à noter que la grosseur des grains d'une poudre ayant passé le tamis de 325 mailles est inférieure à 44 µm.The washing and drying of the washed mixture can be carried out simultaneously. This is how a powder is obtained directly, which passes almost the entire 325 mesh screen, when the washed mixture is treated in a spray dryer. It should be noted that the grain size of a powder having passed the 325 mesh sieve is less than 44 μm.

Le séchage et la pulvérisation du mélange lavé peuvent également être effectués consécutivement. C'est ainsi que l'on peut d'abord sécher le mélange lavé, par exemple dans une étuve, et ensuite désintégrer le mélange séché, par exemple dans un broyeur à marteaux; de cette façon, on obtient également une poudre, qui passe pratiquement dans son entiéreté le tamis de 325 mailles. Si on désire obtenir une poudre plus fine, on traitera le mélange séché dans un moulin à jets d'air, en produisant ainsi une poudre constituée de particules dont le spectre granulométrique est très étroit (0 à 2 µm) et dont la grosseur moyenne des grains est égale à environ 1 µm.Drying and spraying of the washed mixture can also be carried out consecutively. Thus, the washed mixture can first be dried, for example in an oven, and then disintegrate the dried mixture, for example in a hammer mill; in this way, a powder is also obtained, which passes almost in its entirety the 325 mesh screen. If we want to obtain a finer powder, we will treat the dried mixture in an air jet mill, thus producing a powder made up of particles whose particle size spectrum is very narrow (0 to 2 µm) and whose average size grains is approximately 1 µm.

Il est évident que, lorsqu'on effectue la pulvérisation dans un appareil qui n'est pas auto-classifiant, tel le séchoir-atomiseur ou le broyeur à marteaux, il est très utile de tamiser le produit pulvérisé- La Demanderesse recommande dans ce cas de tamiser sur un tamis de

Figure imgb0001
mailles, parce que, comme déjà ditplus haut, il est très facile d'obtenir par le procédé de la présente invention un produit passant pratiquement dans son entièreté un tel tamis et parce qu'il est généralement admis que les propriétés ignifuges d'un produit ignifuge s'améliorent avec la finesse du produit. Cette recommandation n'implique toutefois pas que la mise en oeuvre dans le procédé de la présente invention d'un tamis moins fin, de par exemple 100 mailles, mènerait à un produit de qualité inadmissible.It is obvious that, when spraying is carried out in a device which is not self-classifying, such as the spray dryer or the hammer mill, it is very useful to sift the sprayed product - The Applicant recommends in this case to sieve on a sieve of
Figure imgb0001
mesh, because, as already said above, it is very easy to obtain by the process of the present invention a product passing substantially in its entirety such a sieve and because it is generally accepted that the flame retardant properties of a flame retardant improve with the fineness of the product. This recommendation does not however imply that the implementation in the process of the present invention of a less fine sieve, for example 100 mesh, would lead to a product of unacceptable quality.

Lorsque l'antimoniate de départ contient des impuretés colorantes telles sélénium et tellure, on ajoute avantageusement â la suspension un agent oxydant, de préférence du peroxyde d'hydrogène, en quantité suffisante pour mettre ces impuretés en solution. Très souvent, il suffit d'ajouter environ 5 cc de H202 à 30-35 % pour 1000 g d'antimoine contenu.When the starting antimonate contains coloring impurities such as selenium and tellurium, an oxidizing agent, preferably hydrogen peroxide, is advantageously added to the suspension in an amount sufficient to put these impurities in solution. Very often, it is enough to add approximately 5 cc of H 2 0 2 at 30-35% per 1000 g of antimony contained.

L'invention concerne également les compositions ignifuges obtenues par le procédé suivant l'invention ainsi que les produits ignifugés par addition de ces compositions ignifuges.The invention also relates to the flame retardant compositions obtained by the process according to the invention as well as the flame retardant products by addition of these flame retardant compositions.

Les exemples suivants feront mieux comprendre le procédé de l'invention et ses avantages. Ces exemples illustrent également des compositions ignifuges obtenues par ce procédé, ainsi que des produits ignifugés par addition de ces compositions.The following examples will better understand the process of the invention and its advantages. These examples also illustrate flame retardant compositions obtained by this process, as well as flame retardants by addition of these compositions.

Dans tous ces exemples, la matière de départ est un antimoniate de sodium humide obtenu comme sous-produit dans une installation de raffinage du plomb selon le procédé de Harris.In all of these examples, the starting material is a wet sodium antimonate obtained as a by-product in a lead refining plant according to the Harris process.

Cet antimoniate humide (10 à 12 % en poids d'eau) contient à l'état sec, en % en poids : 48,8 Sb; 9,32 Na; 21,88 H 0 de cristallisation.This wet antimonate (10 to 12% by weight of water) contains in the dry state, in% by weight: 48.8 Sb; 9.32 Na; 21.88 H 0 of crystallization.

Exemple 1Example 1

Cet exemple concerne la préparation d'une composition ignifuge à partir de la matière de départ susdite (antimoniate ex Harris) par le procédé de l'art antérieur mentionné ci-dessus et consistant à broyer l'antimoniate de façon à obtenir un antimoniate très fin.This example relates to the preparation of a flame retardant composition from the above starting material (antimoniate ex Harris) by the process of the prior art mentioned above and consisting in grinding the antimonate so as to obtain a very fine antimonate .

La matière de départ est d'abord séchée et ensuite calcinée à 280° pendant 4 heures pour en chasser la majeure partie de l'eau de cristallisation.The starting material is first dried and then calcined at 280 ° for 4 hours to remove most of the water of crystallization.

L'antimoniate calciné, qui contient 57,74 % en poids d'antimoine,est alors pulvérisé dans un moulin à jets d'air type MC-200 KX de la firme Micro Grinding Ltd. de Suisse. On opère avec une pression de 6,5 bar et l'appareil, qui est auto-classifiant, débite 5 kg de poudre par heure (grosseur moyenne des grains : 1 µm).The calcined antimony, which contains 57.74% by weight of antimony, is then pulverized in an air jet mill type MC-200 KX from the company Micro Grinding Ltd. from Switzerland. We operate with a pressure of 6.5 bar and the device, which is self-classifying, delivers 5 kg of powder per hour (average grain size: 1 µm).

Les propriétés ignifuges de cette poudre sont évaluées par la méthode standardisée de la détermination de l'indice d'oxygène.The flame retardant properties of this powder are evaluated by the standardized method of determining the oxygen index.

On ajoute 5,8 % en poids de cette poudre à une matière plastique constituée de 100 parties de PVC (Solvic 271 GA de la firme Solvay), 36 parties de dioctylphtalate, 5 parties de sulfate tribasique de plomb et 1 partie de stéarate de calcium. Cette matière présente un indice d'oxygène de 30,3.5.8% by weight of this powder is added to a plastic material consisting of 100 parts of PVC (Solvic 271 GA from the company Solvay), 36 parts of dioctylphthalate, 5 parts of tribasic lead sulphate and 1 part of calcium stearate . This material has an oxygen index of 30.3.

Si on remplace dans cette matière les 5,8 % de la poudre d'antimoniate par 4 % de Sb203 ignifuge du commerce (qualité "Blue Star P CHC" de la firme "Compagnie Chimique et Métallurgique Campine" de Belgique; 83,53 % Sb) en produisant ainsi la même teneur en Sb, on obtient un indice d'oxygène de 32,3.If the 5.8% of the antimoniate powder is replaced in this material by 4% of commercial flame retardant Sb 2 0 3 ("Blue Star P CHC" quality from the company "Compagnie Chimique et Métallurgique Campine" from Belgium; 83 , 53% Sb), thus producing the same Sb content, an oxygen index of 32.3 is obtained.

Lorsqu'on ajoute 11,6 % de la poudre d'antimoniate à une matière plastique constituée de 89 parties de polyester (qualité "S.333" de BASF), de 2 parties de Butanox et de 1 partie de octoate de cobalt, on obtient un indice d'oxygène de 26,1. En remplaçant dans cette matière les 11,6 % de la poudre d'antimoniate par 8 % du Sb 0 2 3 ignifuge du commerce susdit, on obtient un indice d'oxygène de 27,4.When 11.6% of the antimoniate powder is added to a plastic material consisting of 89 parts of polyester (quality "S.333" from BASF), 2 parts of Butanox and 1 part of cobalt octoate, obtains an oxygen index of 26.1. By replacing 11.6% of the antimoniate powder in this material with 8% of the flame retardant Sb 0 2 3 from the above-mentioned trade, an oxygen index of 27.4 is obtained.

Exemple 2Example 2

Cet exemple concerne la préparation d'une composition ignifuge à partir de la matière de départ susdite (antimoniate ex Harris) par le procédé de la présente invention.This example relates to the preparation of a flame retardant composition from the above starting material (antimoniate ex Harris) by the process of the present invention.

On met 8 kg d'antimoniate humide en suspension dans une solution constituée de 4 1 d'eau, 1,360 1 de HC1 12 N et 0,68 1 de H 2 SO 4 36 N. On ajoute à cette suspension 0,02 1 de H 2O2 à 30 %. Après 3 heures de réaction à la température ambiante (18°C), on filtre la suspension. On lave la gâteau de filtration avec 13,4 1 d'une solution aqueuse à 0,05 1 de H2SO4 36 N et 0,1 1 de HC1 12 N par litre et ensuite avec 22,3 1 d'eau.8 kg of damp antimoniate are suspended in a solution consisting of 4 1 of water, 1.360 1 of 12 N HCl and 0.68 1 of H 2 SO 4 36 N. To this suspension is added 0.02 1 of H 2 O 2 at 30%. After 3 hours of reaction at room temperature (18 ° C), the suspension is filtered. The filter cake is washed with 13.4 1 of a 0.05 1 aqueous solution of 36 N H 2 SO 4 and 0.1 1 of 12 N HCl per liter and then with 22.3 1 of water.

On sèche le gâteau lavé dans une étuve. On obtient 5,2 kg de produit sec titrant 63,81 % de Sb, 0,18 % de Cl et 0,08 % de Na. Ce produit contient 0,67 % en poids de NaSbO et 99,33 % en poids de Sb205 (valeurs calculées).The washed cake is dried in an oven. 5.2 kg of dry product are obtained, titrating 63.81% of Sb, 0.18% of Cl and 0.08% of Na. This product contains 0.67% by weight of NaSbO and 99.33% by weight of Sb 2 0 5 (calculated values).

Ce produit est pulvérisé dans le moulin à jets d'air de l'exemple 1, à une pression de 6,5 bar. L'appareil débite 30 kg de poudre par heure.This product is sprayed in the air jet mill of Example 1, at a pressure of 6.5 bar. The device delivers 30 kg of powder per hour.

Lorsqu'on ajoute 5,2 % en poids de cette poudre à la matière plastique à base de PVC de l'exemple 1 en produisant ainsi une matière à base de PVC ayant la même teneur en Sb que celles de l'exemple 1, on obtient une matière qui présente un indice d'oxygène de 32,1.When 5.2% by weight of this powder is added to the PVC-based plastic of Example 1, thereby producing a PVC-based material having the same Sb content as that of Example 1, obtains a material which has an oxygen index of 32.1.

Lorsqu'on ajoute 10,5 % en poids de ladite poudre à la matière plastique à base de polyestér de l'exemple 1, en produisant ainsi une matière à base de polyester ayant la même teneur en Sb que celles de l'exemple 1, on obtient une matière qui présente un indice d'oxygène de 28,5.When 10.5% by weight of said powder is added to the polyester-based plastic material of Example 1, thereby producing a polyester-based material having the same Sb content as those of Example 1, a material is obtained which has an oxygen index of 28.5.

Lorsqu'on compare les données des exemples 1 et 2, on voit que :

  • 1°) un mélange d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, obtenu par traitement à l'acide d'antimoniate de sodium, peut être beaucoup plus facilement pulvérisé que l'antimoniate de sodium dont il provient,
  • 2°) à finesse égale, ce mélange présente des propriétés ignifuges qui sont supérieures à celles de l'antimoniate de sodium.
  • 3°) les propriétés ignifuges du produit de l'exemple 2 sont comparables à celles du Sb2O3 ignifuge du commerce pour ce qui concerne l'ignifugation des matières à base de PVC, et supérieures à celles du Sb2O3 ignifuge du commerce pour ce qui concerne l'ignifugation des matières à base de polyesters.
When we compare the data of examples 1 and 2, we see that:
  • 1) a mixture of pentavalent antimony oxide and sodium antimonate obtained by acid treatment of sodium antimonate, may be much more easily sprayed as sodium antimonate which he p rovient,
  • 2) for equal fineness, this mixture has flame retardant properties which are superior to those of sodium antimonate.
  • 3) the flame retardant properties of the product of Example 2 are comparable to those of commercial flame retardant Sb 2 O 3 with regard to the flame retardancy of PVC-based materials, and superior to those of flame retardant Sb 2 O 3 from trade with regard to the fireproofing of polyester-based materials.

Exemple 3Example 3

Cet exemple concerne, comme l'exemple 2, la préparation d'une composition ignifuge à partir de la matière de départ susdite (antimoniate ex Harris) par le procédé de la présente invention.This example, like example 2, relates to the preparation of a flame retardant composition from the aforementioned starting material (antimoniate ex Harris) by the process of the present invention.

On met 7,15 kg d'antimoniate humide en suspension dans une solution constituée de 4,3 1 d'eau et de 2,86 1 de HCI 12 N. On agite pendant 3 heures à la température ambiante (18°C). On filtre et on lave le gâteau de filtration avec 12,45 litres d'une solution aqueuse à 0,16 1 de HCl 12 N par litre et ensuite avec 20,9 1 d'eau. On sèche le gâteau lavé dans une étuve. On obtient 4,647 kg de produit sec titrant en % en poids : 61,74 Sb, 0,61 Na et 0,17 HCl. Ce produit contient 5,24 % en poids de NaSbO 3 et 94,76 % en poids de Sb2O5 (valeurs calculées). Après désintégration du produit séché dans un broyeur à marteaux, on le tamise sur un tamis de 325 mailles. La fraction ayant passé le tamis (99,7 %) est utilisée pour ignifuger la matière plastique à base de PVC des exemples 1 et 2. A cette matière plastique, on ajoute 5,4 % en poids de cette fraction ayant passé le tamis de 325 mailles en produisant ainsi une matière plastique à base de PVC ayant la même teneur en Sb que celles des exemples 1 et 2. Cette matière plastique présente un indice d'oxygène de 31,6. Quoique de 0,7 unités inférieur à celui obtenu dans l'exemple 2, cet indice, obtenu à l'aide d'une composition ignifuge assez grossière, est encore de 1,3 unités supérieur à celui obtenu dans l'exemple 1 avec de l'antimoniate très fin.7.15 kg of moist antimoniate are suspended in a solution consisting of 4.3 l of water and 2.86 l of 12N HCl. The mixture is stirred for 3 hours at room temperature (18 ° C). It is filtered and the filter cake is washed with 12.45 liters of an 0.16 1 aqueous solution of 12 N HCl per liter and then with 20.9 1 of water. The washed cake is dried in an oven. 4.647 kg of dry product are obtained, titrating in% by weight: 61.74 Sb, 0.61 Na and 0.17 HCl. This product contains 5.24% by weight of NaSbO 3 and 94.76% by weight of Sb 2 O 5 (calculated values). After the dried product has disintegrated in a hammer mill, it is sieved through a 325 mesh screen. The fraction having passed the sieve (99.7%) is used to flame retard the PVC-based plastic material of Examples 1 and 2. To this plastic material, 5.4% by weight of this fraction having passed the sieve is added. 325 meshes, thereby producing a PVC-based plastic material having the same Sb content as those of Examples 1 and 2. This plastic material has an oxygen index of 31.6. Although 0.7 units lower than that obtained in Example 2, this index, obtained using a fairly coarse flame retardant composition, is still 1.3 units higher than that obtained in Example 1 with the very fine antimony.

Exemple 4Example 4

Cet exemple concerne également la préparation d'une composition ignifuge à partir de la matière de départ susdite (antimoniate ex Harris) par le procédé de la présente invention.This example also relates to the preparation of a flame retardant composition from the above-mentioned starting material (antimoniate ex Harris) by the process of the present invention.

On met 9 kg d'antimoniate humide en suspension dans une solution constituée de 5 1 d'eau et de 1,17 1 de H2SO4 36 N. On ajoute à la suspension 0,023 1 de H2O2 à 30 % et on agite la suspension pendant 1 heure à 80°C. On filtre et on lave le gâteau de filtration avec 11,6 1 d'une solution aqueuse à 0,06 1 de H2SO4 36 N par litre et ensuite avec 15,4 1 d'eau. On sèche le gâteau lavé dans une étuve. On obtient 5,381 kg de produit sec titrant en % en poids : 61,78 Sb, 3,61 Na et 0,02 Cl. Ce produit contient 31 % en poids de NaSbO3 et 69 % en poids de Sb 0 (valeurs calculées).9 kg of wet antimoniate are suspended in a solution consisting of 5 1 of water and 1.17 1 of H 2 SO 4 36 N. 0.023 1 of H 2 O 2 at 30% is added to the suspension and the suspension is stirred for 1 hour at 80 ° C. The filter is filtered and the filter cake is washed with 11.6 1 of a 0.06 1 aqueous solution of H 2 SO 4 36 N per liter and then with 15.4 1 of water. The washed cake is dried in an oven. 5.381 kg of dry product are obtained, titrating in% by weight: 61.78 Sb, 3.61 Na and 0.02 Cl. This product contains 31% by weight of NaSbO 3 and 69% by weight of Sb 0 (calculated values) .

Ce produit est pulvérisé dans le moulin à jets d'air de l'exemple 1, à une pression de 6,5 bar. L'appareil débite 30 kg de poudre par heure.This product is sprayed in the air jet mill of Example 1, at a pressure of 6.5 bar. The device delivers 30 kg of powder per hour.

Lorsqu'on ajoute 5,4 % en poids de ce produit à la matière plastique à base de PVC de l'exemple 1 en produisant ainsi une matière à base de PVC ayant la même teneur en Sb que celles de l'exemple 1, on obtient une matière qui présente un indice d'oxygène de 31,7.When 5.4% by weight of this product is added to the PVC-based plastic of Example 1, thereby producing a PVC-based material having the same Sb content as that of Example 1, obtains a material which has an oxygen index of 31.7.

Lorsqu'on compare les données des exemples 2 et 4, on voit que la haute teneur en sodium (NaSbO3) du produit obtenu dans l'exemple 4 semble avoir une influence défavorable sur les propriétés ignifuges de ce produit. Toutefois, l'indice d'oxygène de ce produit à haute teneur en sodium est encore de 1,4 unités supérieur à celui obtenu dans l'exemple 1 avec de l'antimoniate très fin.When comparing the data of Examples 2 and 4, it is seen that the high sodium content (NaSbO 3 ) of the product obtained in Example 4 seems to have an unfavorable influence on the flame retardant properties of this product. However, the oxygen index of this product with a high sodium content is still 1.4 units higher than that obtained in Example 1 with very fine antimonate.

Exemple 5Example 5

Dans cet exemple, on décrit deux essais comparatifs illustrant l'influence de la température de réaction sur la teneur en sodium du produit obtenu par le procédé de l'invention.In this example, two comparative tests are described illustrating the influence of the reaction temperature on the sodium content of the product obtained by the process of the invention.

Dans un premier essai, on met 0,85 kg d'antimoniate humide en suspension dans une solution constituée de 0,5 1 d'eau et de 0,34 1 de HC1 12 N. On agite la suspension pendant 1 heure à 80°C. On filtre et on lave le gâteau de filtration avec 0,54 1 de HC1 1,5 N et ensuite 0,9 1 d'eau. On sèche le gâteau lavé dans une étuve. On obtient 0,593 kg de produit sec titrant en % en poids : 60 Sb, 4,43 Na et 1,03 Cl. Ce produit contient 39,1 % en poids de NaSbO et 60,9 % de Sb2O5 (valeurs calculées).In a first test, 0.85 kg of damp antimoniate is suspended in a solution consisting of 0.5 1 of water and 0.34 1 of 12N HCl. The suspension is stirred for 1 hour at 80 ° vs. It is filtered and the filter cake is washed with 0.54 l of 1.5 N HCl and then 0.9 l of water. The washed cake is dried in an oven. 0.593 kg of dry product is obtained, titrating in% by weight: 60 Sb, 4.43 Na and 1.03 Cl. This product contains 39.1% by weight of NaSbO and 60.9% of Sb 2 O 5 (calculated values).

Dans le second essai, on opère de la même façon si ce n'est que l'on effectue la réaction à la température ambiante. On obtient 0,57 kg de produit sec titrant en % en poids : 64,9 Sb, 0,7 Na et 0,27 Cl. Ce produit contient 5,7 % en poids de NaSbO et 94,3 % en poids de Sb2O5 (valeurs calculées).In the second test, the procedure is the same except that the reaction is carried out at room temperature. 0.57 kg of dry product is obtained titrating in% by weight: 64.9 Sb, 0.7 Na and 0.27 Cl. This product contains 5.7% by weight of NaSbO and 94.3% by weight of Sb 2 O 5 (calculated values).

Dans le procédé de l'invention, il importe donc d'opérer à la température ambiante pour obtenir un produit à faible teneur en sodium.In the process of the invention, it is therefore important to operate at room temperature to obtain a product with a low sodium content.

Exemple 6Example 6

Dans cet exemple, on décrit deux essais comparatifs illustrant l'influence des conditions de lavage du gâteau de filtration sur la teneur en sodium du produit obtenu par le procédé de l'invention.In this example, two comparative tests are described illustrating the influence of the conditions for washing the filter cake on the sodium content of the product obtained by the process of the invention.

On met 0,85 kg d'antimoniate humide en suspension dans une solution constituée de 0,5 1 d'eau et de 0,34 1 de HCl 12 N. On agite la suspension pendant 4 heures à la température ambiante (19°C). On divise alors la suspension en deux portions à peu près égales.0.85 kg of moist antimoniate is suspended in a solution consisting of 0.5 l of water and 0.34 1 of 12N HCl. The suspension is stirred for 4 hours at room temperature (19 ° C. ). The suspension is then divided into two approximately equal portions.

On filtre la première portion et on lave le gâteau de filtration avec 1,27 1 d'eau. On sèche le gâteau lave dans une étuve. On obtient 0,252 kg de produit sec titrant en % en poids : 63 Sb, 1,92 Na et 0,3 Cl. Ce produit contient 16,1 % en poids de NaSbO 3 et 83,9 % en poids de Sb2O5 (valeurs calculées).The first portion is filtered and the filter cake is washed with 1.27 l of water. The washed cake is dried in an oven. 0.252 kg of dry product is obtained, titrating in% by weight: 63 Sb, 1.92 Na and 0.3 Cl. This product contains 16.1% by weight of NaSbO 3 and 83.9% by weight of Sb 2 O 5 (calculated values).

On filtre la seconde portion et on lave le gâteau de filtration d'abord avec 0,45 1 d'une solution aqueuse à 0,16 1 de HCl 12 N par litre et ensuite avec 1,13 1 d'eau. On sèche le gâteau lavé dans une étuve. On obtient 0,294 kg de produit sec titrant en % en poids : 63,48 Sb, 0,43 Na et 0,18 Cl. Ce produit contient 3,6 % en poids de NaSbO3 et 96,4 % en poids de Sb2O5 (valeurs calculées).The second portion is filtered and the filter cake is washed first with 0.45 1 of an aqueous solution of 0.16 1 of 12 N HCl per liter and then with 1.13 1 of water. The washed cake is dried in an oven. 0.294 kg of dry product is obtained, titrating in% by weight: 63.48 Sb, 0.43 Na and 0.18 Cl. This product contains 3.6% by weight of NaSbO 3 and 96.4% by weight of Sb 2 O 5 (calculated values).

Dans le procédé de l'invention, il importe donc de laver le gâteau de filtration d'abord avec une solution acide pour obtenir un produit à faible teneur en sodium.In the process of the invention, it is therefore important to wash the filter cake first with an acid solution to obtain a product with a low sodium content.

Il est à noter que dans les exemples 2 à 6 décrits ci-dessus, on a retrouvé dans le produit final plus de 96 % de l'antimoine mise en oeuvre au départ, ce qui veut dire que dans le procédé de l'invention les pertes d'antimoine sont très faibles.It should be noted that in Examples 2 to 6 described above, more than 96% of the antimony used was found in the final product, which means that in the process of the invention the antimony losses are very small.

Il est également à noter que l'antimoniate ex Harris utilisé comme matière de départ dans ces exemples, est un antimoniate obtenu à haute température et par conséquent peu réactif. Il va donc de soi que l'on peut traiter par le procédé de la présente invention tout antimoniate de sodium, qu'il soit obtenu à haute température ou par voie humide.It should also be noted that the ex Harris antimonate used as starting material in these examples is an antimonate obtained at high temperature and therefore not very reactive. It therefore goes without saying that any sodium antimoniate can be treated by the process of the present invention, whether it is obtained at high temperature or by the wet method.

Claims (21)

1. Procédé pour préparer une composition ignifuge à partir d'antimoniate de sodium, caractérisé en ce qu'on fait réagir l'antimoniate avec une solution acide de façon à transformer une fraction de l'antimoniate en oxyde d'antimoine pentavalent, en produisant ainsi un mélange constitué d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, on sépare le mélange ainsi produit de la solution, on sèche et on pulvérise ce mélange.1. Method for preparing a flame-retardant composition from sodium antimonate, characterized in that the antimoniate is reacted with an acid solution so as to convert a fraction of the antimoniate into pentavalent antimony oxide, producing thus a mixture of pentavalent antimony oxide and sodium antimonate, the mixture thus produced is separated from the solution, dried and sprayed with this mixture. 2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise en tant que solution acide, une solution aqueuse d'acide chlorhydrique et/ou d'acide sulfurique et/ou d'acide nitrique.2. Method according to claim 1, characterized in that an aqueous solution of hydrochloric acid and / or sulfuric acid and / or nitric acid is used as the acid solution. 3. Procédé selon la revendication 2, caractérisé en ce que la concentration de la solution acide est comprise entre 1 et 5 N.3. Method according to claim 2, characterized in that the concentration of the acid solution is between 1 and 5 N. 4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce qu'on fait réagir l'antimoniate de sodium avec une quantité d'acide allant de 1 à 1,35 fois la quantité stoechiométrique.4. Method according to claim 1, 2 or 3, characterized in that the sodium antimonate is reacted with an amount of acid ranging from 1 to 1.35 times the stoichiometric amount. 5. Procédé selon la revendication 4, caractérisé en ce qu'on transforme au moins 60 % de l'antimoniate en oxyde.5. Method according to claim 4, characterized in that at least 60% of the antimonate is converted into oxide. 6. Procédé selon la revendication 5, caractérisé en ce qu'on transforme au moins 95 % de l'antimoniate en oxyde.6. Method according to claim 5, characterized in that it transforms at least 95% of the antimonate into oxide. 7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on met l'antimoniate de sodium en suspension dans la solution acide, la teneur en antimoniate de sodium de la suspension étant de 200 à 900 g/1.7. Method according to any one of the preceding claims, characterized in that the sodium antimonate is suspended in the acid solution, the sodium antimonate content of the suspension being from 200 to 900 g / 1. 8. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on effectue la réaction à la température ambiante.8. Method according to any one of the preceding claims, characterized in that the reaction is carried out at room temperature. 9. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on lave le mélange, séparé de la solution, d'abord avec une solution acide diluée et ensuite avec de l'eau.9. Method according to any one of the preceding claims, characterized in that the mixture, separated from the solution, is washed first with a dilute acid solution and then with water. 10. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on utilise de l'antimoniate de sodium contenant des impuretés colorantes et on ajoute à la solution acide un agent oxydant en quantité suffisante pour oxyder ces impuretés.10. Method according to any one of the preceding claims, characterized in that sodium antimonate containing coloring impurities is used and an oxidizing agent is added to the acid solution in an amount sufficient to oxidize these impurities. 11. Procédé selon la revendication 10, caractérisé en ce qu'on utilise du peroxyde d'hydrogène en tant qu'agent oxydant.11. Method according to claim 10, characterized in that hydrogen peroxide is used as an oxidizing agent. 12. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce qu'on utilise comme antimoniate de sodium de départ, de l'antimoniate obtenu à haute température.12. Method according to any one of the preceding claims, characterized in that the starting antimoniate of sodium is antimonate obtained at high temperature. 13. Procédé selon la revendication 12, caractérisé en ce qu'on utilise l'antimoniate de sodium obtenu comme sous-produit au raffinage alcalin de plomb antimonifère.13. Method according to claim 12, characterized in that the sodium antimonate obtained is used as a by-product in the alkaline refining of antimoniferous lead. 14. Composition ignifuge constituée d'un mélange d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, caractérisé en ce que ce mélange est obtenu en faisant réagir de l'antimoniate de sodium avec de l'acide.14. Flame retardant composition consisting of a mixture of pentavalent antimony oxide and sodium antimonate, characterized in that this mixture is obtained by reacting sodium antimonate with acid. 15. Composition selon la revendication 14, caractérisé en ce qu'elle contient au moins 60 % en poids de Sb 0 .15. Composition according to claim 14, characterized in that it contains at least 60% by weight of Sb 0. 16. Composition selon la revendication 15, caractérisé en ce qu'elle contient au moins 95 % en poids de Sb2O5.16. Composition according to claim 15, characterized in that it contains at least 95% by weight of Sb 2 O 5 . 17. Produit ignifugé par addition d'un mélange d'oxyde d'antimoine pentavalent et d'antimoniate de sodium, caractérisé en ce que ce mélange est obtenu en faisant réagir de l'antimoniate de sodium avec de l'acide.17. Flame retardant product by addition of a mixture of pentavalent antimony oxide and sodium antimonate, characterized in that this mixture is obtained by reacting sodium antimonate with acid. 18. Produit selon la revendication 17, caractérise en ce que le mélange contient au moins 60 % en poids de Sb 0 .18. Product according to claim 17, characterized in that the mixture contains at least 60% by weight of Sb 0. 19. Produit selon la revendication 18, caractérisé en ce que le mélange contient au moins 95 % en poids de Sb2 O5.19. Product according to claim 18, characterized in that the mixture contains at least 95% by weight of Sb 2 O 5 . 20. Produit selon la revendication 17, 18 et 19, caractérisé en ce qu'il est à base de chlorure de polyvinyl.20. Product according to claim 17, 18 and 19, characterized in that it is based on polyvinyl chloride. 21. Produit selon la revendication 17, 18 et 19, caractérisé en ce qu'il est à base de polyester.21. Product according to claim 17, 18 and 19, characterized in that it is based on polyester.
EP80200808A 1979-09-05 1980-08-28 Process for preparing a fireproofing composition from sodium antimonate, and composition so obtained Expired EP0025246B1 (en)

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EP0134708A3 (en) * 1983-08-16 1986-05-14 Nissan Chemical Industries Ltd. Process for preparing colloidal solution of antimony pentoxide
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EP0136120A3 (en) * 1983-09-10 1985-12-18 Nissan Chemical Industries Ltd. Flame retardant for halogen-containing vinyl resins

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ZA805283B (en) 1981-08-26
LU81649A1 (en) 1981-04-17
CA1136789A (en) 1982-11-30
DE3065889D1 (en) 1984-01-19
JPS648014B2 (en) 1989-02-10
MX155813A (en) 1988-05-06
JPS5659851A (en) 1981-05-23
EP0025246B1 (en) 1983-12-14
US4362658A (en) 1982-12-07

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